Recherches sur la formation et la transformation des esters LXXVII [1]. Etude à l'aide de H2[18O] de la scission de quelques monoesters phosphoreux et de l'acide propargyl-benzènephosphonique

(1) Monopotassium phosphite KH₂PO₃ heated at 300°C with CO[¹⁸O] exchanges one atom of oxygen after 3 hours, one to two atoms after 6 hours, and its three O atoms after 12 hours; the probable mecanism of this exchange is discussed. When the same treatment is carried out in the presence of o-phenylene diamine hydrochloride, the exchange is total (three O) after 3 hours at 300°C. Treated by this last procedure, benzenephosphonic acid C₆H₅PO(OH)₂ undergoes equally a total exchange of its O atoms in 3 hours.     

Mechanistic study of thermal behavior and combustion performance of epoxy resins: I homopolymerized TGDDM

Tetraglycidyl 4,4′-diaminodiphenylmethane (TGDDM) undergoes homopolymerization on heating. Intramolecular reactions which compete with crosslinking favor the formation of cyclic structures with increasing thermal and fire resistance of the resin, whereas physical mechanical properties tend to decrease. The mechanism of thermal decomposition of TGDDM is studied by thermogravimetry, differential scanning calorimetry and thermal volatilization analysis with characterization of volatiles evolved and residue left. Thermal degradation of poly-(TGDDM) starts at 260°C with elimination of water from secondary alcoholic groups which is a typical pathway for epoxy resin degradation. Resulting unsaturations weaken bonds in the β-position and provoke the first chain breaking at allyl–amine and allyl–either bonds. With increasing temperature, saturated alkyl–ether bonds and alkyl carbon–carbon bonds are broken first, followed by the most stable alkyl–aryl bonds at T>365°C. The combustion performance of TGDDM is discussed on the basis of the thermal degradation behavior.     

POLARIZED OPTICAL PROPERTIES OF PHYCOBILISOMES FROM Anabaena, Nostoc and Synechococcus

Polarized absorption, photoacoustic, fluorescence excitation and fluorescence emission spectra of phycobilisomes were measured when embedded in polyvinyl alcohol films. The phycobilisomes were isolated from the following organisms: Anabaena cylindrica, Nostoc punctiforma and Synechococcus elongatus. The ratio of photoacoustic spectra to absorption was taken as a measure of thermal dissipation of excitation energy. The isotropic samples and those oriented by the film stretching were investigated. The stretching of the sample strongly influences the efficiency of excitation energy transfer occurring among biliproteins in phycobilisomes, as is seen from the dramatic changes in the fluorescence and thermal dissipation spectra. The effect of stretching the film depends on the shape of phycobilisomes and on the strength of interactions between biliproteins in phycobilisomes.     

ETUDE EN SPECTROMETRIE DE MASSE DE PHOSPHONATES ENYNIQUES ET DE β-CETOPHOSPHONATES-γ, δ-ETHYLENIQUES

The mass spectrometric study of acetylenic dialkylphosphonates (I) and of γ, δ-éthylenic-β-ketophosphonates (II) is characterised by rearrangement processes of the phosphorylated group and cleavage of the phosphorus-carbon bond. The fragmentation patterns of compounds II were identical to those found for I by loss of water.     

Theoretical analysis of the three-dimensional structure of tetrathiolato iron complexes

The three-dimensional structures of a number of [M(SR)(4)](n-) complexes, where M is a 3d transition metal and R is an alkyl or aryl group, have been analyzed using density functional theory (DFT). Special attention is paid to the Fe(II)/Fe(III) mimics of rubredoxin. The Fe(II) model complex [Fe(SCH(3))(4)](2-) has an equilibrium conformation with D2d symmetry. The DFT energy has been decomposed into contributions for ligand-ligand and metal-ligand interactions. The latter contribution is analyzed with the angular overlap model (AOM) and constitutes the dominant stereospecific interaction in the Fe(II) complex. The sulfur lone-pair electrons exert anisotropic pi interactions on the 3d(6) shell of Fe(II), which are controlled by the torsion angles, omega(i), for the rotations of the S(i)-C(beta) bonds around the Fe-S(i) axes. In contrast, the pi interactions acting on the high-spin 3d(5) shell of Fe(III) are isotropic. As a consequence, the stereochemistry of the Fe(III) complexes is determined by the Coulomb repulsions between the ligands and has S(4) symmetry. The electrostatic repulsions between the lone pairs of the sulfurs are an essential component of the ligand-ligand interaction. The lone-pair repulsions distort the 90 degree angle SFeS' angles (delta + delta(t)) and give rise to a correlation between delta and omega, which is confirmed by crystallographic data. Both the Fe(II) and Fe(III) complexes exhibit structural bistability due to the presence of low-lying equilibrium conformations with S(4) symmetry in which the complex can be trapped by the crystalline host.     

Recherches sur la formation et la transformation des esters LXXIII Sur la préparation d'acides ω-[aryl (ou aralcoyl ou alcoyl) carbamylamino]-alcoylphosphoriques et sur leur vitesse de scission à divers pH

N-Aryl(or aralkyl or alkyl)carbamoyl-aminoalkyl phosphoric monoesters have been prepared by the reaction of isocyanates R′-N?C?O on the corresponding amino-alkylphosphoric monoesters H₂N? R? OPO₃H₂ in the presence of 2 equivalents of NaOH. The rates of scission of the phosphoric monoester group and occasionally of the phenylcarbamoylamino group of these monoesters have been studied at 100°, in solutions 0.1M in ester and at various pH.     

Zur Theorie der harmonischen Differentialformen

Generalizing harmonic differential forms (rot =0, div =0 in M, M being a smooth riemannian manifold with boundary) of first and second kind (=0 and *=0 on M resp.) within the framework of Hilbert space notation, it is possible to extend the meaning of the boundary conditions to non-smooth boundaries. It turns out that in this case the classical result is still valid for certain open subregions G of M: The dimension of the space of harmonic differential forms of second kind is given by the q-th Betti number of G; *-duality leads to the respective result for harmonic differential forms of first kind.     

Coexistence and harvesting control policy in a food chain model with mutual defense of prey

A model is proposed to understand the dynamics in a food chain (one predator‐two prey). Unlike many approaches, we consider mutualism (for defense against predators) between the two groups of prey. We investigate the conditions for coexistence and exclusion. Unlike Elettreby's (2009) results, we show that prey can coexist in the absence of predators (as expected since there is no competition between prey). We also show the existence of Hopf bifurcation and limit cycle in the model, and numerically present bifurcation diagrams in terms of mutualism and harvesting. When the harvest is practiced for profit making, we provide the threshold effort value that determines the profitability of the harvest. We show that there is zero profit when the constant effort is applied. Below (resp. above) , there will always be gain (resp. loss). In the case of gain, we provide the optimal effort and optimal steady states that produce maximum profit and ensure coexistence. Recommendations for resource managers As a result of our investigation, we bring the following to the attention of management:

• 1. In the absence of predators, different groups of prey can coexist if they mutually help each other (no competition among them).
• 2. There is a maximal effort to invest in order to gain profit from the harvest. Above , the investment will result in a loss.
• 3. In the case of profit from harvest, policy makers should recommend the optimal effort to be applied and the optimal stock to harvest. This will guarantee maximum profit while ensuring sustainability of all species.

     

Time-resolved torsional relaxation of spider draglines by an optical technique

The sensitivity of the torsional pendulum demonstrates the self-shape-memory effect in different types of spider draglines. Here we report the time-resolved noncovalent bonds recovery in the protein structure. The torsional dynamics of such multilevel structure governed by reversible interactions are described in the frame of a nested model. Measurement of three different relaxation times confirms the existence of three energy storage levels in such two protein spidroin systems. Torsion opens the way to further investigations towards unraveling the tiny torque effects in biological molecules.     

The versatility of pentalene coordination to transition metals: a density functional theory investigation

DFT calculations with full geometry optimization have been carried out on a series of real and hypothetical compounds of the type [CpM(C8H6)], [(CO)3M(C8H6)], [M(C8H6)2], [(CpM)2(C8H6)], [[(CO)3M]2(C8H6)], and [M2(C8H6)2] (M = transition metal). The bonding in all the currently known compounds is rationalized, as well as in the (so far) hypothetical stable complexes. Depending on the electron count and the nature of the metal(s), eta2 (predicted), eta3, eta5, eta8, or intermediate coordination modes can be adopted. In the case of the mononuclear species, the most favored closed-shell electron counts are 18 and 16 metal valence electrons (MVE). In the case of the dinuclear species, an electron count of 34 MVEs is most favored. However, other electron counts can be stabilized, especially in the case of dinuclear complexes. Coordinated pentalene should most often be considered as formally being a dianion, but sometimes as a neutral ligand. In the former case it can behave as an aromatic species made of two equivalent fused rings, as a C5 aromatic ring connected to an allylic anion, or even as two allylic anions bridged by a C7=C8 double bond. In the latter case, it can behave as a bond-alternating cyclic polyene or as a C5 aromatic ring connected to an allylic cation.